CN101263258A - Method for treating surfaces - Google Patents

Method for treating surfaces Download PDF

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Publication number
CN101263258A
CN101263258A CNA2006800339565A CN200680033956A CN101263258A CN 101263258 A CN101263258 A CN 101263258A CN A2006800339565 A CNA2006800339565 A CN A2006800339565A CN 200680033956 A CN200680033956 A CN 200680033956A CN 101263258 A CN101263258 A CN 101263258A
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weight
water
copolymer
fit
particulate form
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O·埃利萨尔德
M·施密特
M·伯特
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BASF SE
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BASF SE
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/70—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
    • D06M15/71—Cooling; Steaming or heating, e.g. in fluidised beds; with molten metals
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01—Stain or soil resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The invention relates to a method for treating surfaces. Said method is characterised in that the surfaces are treated with (a) at least one hydrophobic agent, (b) at least one cross-linked organic copolymer in a particle form, (c) at least one film-forming copolymer comprising epoxide groups, NH-CH2OH-groups or acetoacetyl groups, (d) optionally, one or several emulsifiers, and finally, dried after treating.

Description

The method of treatment surface
The present invention relates to a kind of method of treatment surface, it comprises with the described surface of following mass treatment:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to, one or more emulsifying agents,
Be dried subsequently.
The invention still further relates to treated surface.The invention still further relates to preferred aqueous formulation and production method according to preferred aqueous formulation of the present invention.
Thereby people make it antifouling or be difficult to the contaminated obvious interest that has at least to treatment surface always over several years.Numerous methods relate to provides the have texture surface of (texturing), for example has the surface that is spaced apart of high projection of 5 to 100 μ m and 5 to 200 μ m.The surface has been given the texture of simulation nelumbium, for example referring to WO 96/04123 and US 3,354,022.Yet, this method always wise and be unsuitable for handling fabric face.
EP 1 283 296 discloses the coated fabric laminated structure, and coating is made by as described below: fabric for example is selected from potato starch and comprises adhesive, fluorinated polymer and if the matrix of the words auxiliary agent that is fit to applies such as the finely divided material (diameter is (at least 80 weight % finely divided material) in 0.5 to 100 mu m range) of silica gel, silica flour or kaolinic oxidation material and 20 weight % to 50 weight % with 50 weight % to 80 weight % at least a.
WO 04/74568 discloses a kind of method by coming the finish fabric material with at least a liquid, aqueous processing that comprises the organic or inorganic solid of at least a organic polymer and at least a particulate form, and wherein the organic or inorganic solid is present in the liquid with the mark of 5.5g/l at least.Silica gel, particularly pyrolysismethod silica gel is preferably the solid of particulate form.
Yet therefore, in liquid, aqueous, have temperature variant specific solubility as the potato starch of being recommended among the EP 1 283 296, diameter that can't Optimal Control potato starch particle in applying operation.Especially under the situation of the inoganic solids of for example silica gel, observe certain agglomeration tendency, this is to applying unfavorable and making the setting of organizational parameter more difficult.
Observe the fabric that applies by preceding method in many cases in addition and have insufficient washability sometimes.For example, if washing has the fabric of sweat stain, the anti-fouling effect that then will observe after the washing for the first time reduces, and several times after washing cycle anti-fouling effect disappear in fact.
The purpose of this invention is to provide a kind of method of having avoided the treatment surface of above-mentioned shortcoming, particularly about handling the method for fabric face.The present invention also aims to provide the treated surface of having avoided above-mentioned shortcoming and having presented good soil resistance.
We have found that this purpose realizes by the defined method of beginning.
The inventive method at be the surface.Surface for the purpose of the present invention can be constituted and belonged to any needed article by any needed material.The preferred surface that constitutes by fibrous material such as paper, plate, leather, dermatine, Alcantara, and the surface is the surface of fabric more specifically.
For the purpose of the present invention, fabric is fabric fibre, fabric intermediate and finished product and by the finished product of its manufacturing and the fabric that is used for clothing industry, and it also comprises for example carpet and other household fabric and the fabric construction that is used for industrial purposes.These structures comprise the prepattern structure, as staple fibre; Linear structure is as linen thread, long filament, yarn, long fiber crops, cord, lace, roll band, rope; And three-dimensional structure, as felt, weaven goods, nonwoven and liner.For the purpose of the present invention, fabric can be natural origin, and example is cotton, wool or flax; Or synthetic source, example is polyester, polyester blend fabric, polyamide BLENDED FABRIC, polyacrylonitrile, triacetate, acetic acid esters, Merlon, polypropylene, polyvinyl chloride, polyester microfiber and the glass fabric of polyamide, polyester, modification.The preferred especially fabric that constitutes by cotton.
For the purpose of the present invention, the laminated structure of fabric can have a surface (side, front) of handling by the inventive method, and does not handle by the inventive method on another surface, or two surfaces (side, front) all can be handled by the inventive method.For example, in some clothes, for example may reasonably be to handle outer surface, and handle by the inventive method on interior (towards health) surface by the inventive method such as Work Clothes; On the other hand, may reasonably be that all handle by the inventive method on the two sides (obverse and reverse) of some technical fabrics such as awning.
Handle with following material according to the present invention:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to one or more emulsifying agents.
One embodiment of the invention comprise from following material selects water-repelling agent:
(a1) Halogen (halous) organic (being total to) polymer,
(a2) paraffin and
(a3) per molecule has at least one C 10-C 60The compound of alkyl.
Useful Halogen organic (being total to) polymer (a1) comprises for example chlorination, free radical (be total to) polymerization of the preferably single or many halogenations by one or more of (being total to) polymer of especially fluoridizing, described (being total to) polymer, preferred chlorination, (copolymerization) monomer of more preferably fluoridizing prepares.
Halogenation very particularly preferably (copolymerization) monomer is for example vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, a hexafluoropropene of Fluorine containing olefine, as fluoridizing or perfluorinate C of describing among for example US 2,592,069 and the US 2,732,370 3-C 11The vinyl esters of carboxylic acid, as US 2,642,416, describe among US 3,239,557 and the US 3,462,296 fluoridize or perfluorinated alcohols is for example fluoridized or perfluorinate C 3-C 14(methyl) acrylate of alkylol, for example HO-CH 2-CH 2-CF 3, HO-CH 2-CH 2-C 2F 5, HO-CH 2-CH 2-n-C 3F 7, HO-CH 2-CH 2-iso-C 3F 7, HO-CH 2-CH 2-n-C 4F 9, HO-CH 2-CH 2-n-C 6F 13, HO-CH 2-CH 2-n-C 8F 17, HO-CH 2-CH 2-O-n-C 6F 13, HO-CH 2-CH 2-O-n-C 8F 17, HO-CH 2-CH 2-n-C 10F 21, HO-CH 2-CH 2-n-C 12F 25(methyl) acrylate.
For example (methyl) acrylic acid and/or (methyl) acrylic acid C 1-C 20The copolymer of the ester of Arrcostab or (methyl) glycidyl acrylate and formula I:
Figure A20068003395600071
Wherein
R 1Be hydrogen, CH 3, C 2H 5,
R 2Be CH 3, C 2H 5,
X is the integer of 4-12, the integer of 6-8 preferably,
Y is the integer of 1-11, the integer of 1-6 preferably,
Perhaps the copolymer of the vinyl esters of (methyl) glycidyl acrylate and fluorinated carboxylic also can be used as Halogen organic (being total to) polymer (a).
Useful Halogen organic (being total to) polymer (a) also comprise fluoridize, perfluorinate C especially 3-C 12(methyl) acrylate of alkylol and halogenation C not 1-C 20The copolymer of (methyl) acrylate of alcohol is describedly fluoridized, perfluorinate C especially 3-C 12Alkylol for example is HO-CH 2-CH 2-CF 3, HO-CH 2-CH 2-C 2F 5, HO-CH 2-CH 2-n-C 3F 7, HO-CH 2-CH 2-iso-C 3F 7, HO-CH 2-CH 2-n-C 4F 9, HO-CH 2-CH 2-n-C 6F 13, HO-CH 2-CH 2-n-C 8F 17, HO-CH 2-CH 2-O-n-C 6F 13, HO-CH 2-CH 2-O-n-C 8F 17, HO-CH 2-CH 2-n-C 10F 21, HO-CH 2-CH 2-n-C 12F 25, described not halogenation C 1-C 20(methyl) acrylate of alcohol for example is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid n-propyl, (methyl) 2-ethylhexyl acrylate, (methyl) acrylic acid n-octyl, (methyl) acrylic acid ester in the positive last of the ten Heavenly stems, (methyl) acrylic acid dodecyl ester, (methyl) acrylic acid n-eicosane base ester.
About the summary of the fluorinated polymer that can be used as Halogen organic (being total to) polymer (a1) and copolymer referring to for example M.Lewin etc., Chemical Processing of Fibers and Fabrics (" chemical process of fiber and fabric "), Part B, the 2nd volume, Marcel Dekker, New York (1984), the 172nd page and content and 178-182 page or leaf subsequently.
Other (being total to) polymer of fluoridizing as Halogen organic (being total to) polymer (a1) for example are described among the DE199 120 810.
Method of the present invention can use a kind of Halogen (being total to) polymer (a1) or multiple different Halogen (being total to) polymer (a1) to carry out.
Halogen (being total to) polymer (a1) preferably is used to carry out method of the present invention with uncrosslinked form, but it can be during drying crosslinked.
Other water-repelling agent (a) that is fit to is paraffin (a2).Paraffin (a2) at room temperature can be liquid or solid for example, and has natural or preferred synthetic source.Preferred paraffin (a2) is synthetic paraffin, f-t synthetic wax for example, for example use the high density polyethylene waxes of Ziegler-Natta catalyst or metallocene catalysts, and the acid number of measuring according to DIN 53402 is the high density polyethylene waxes through partial oxidation of 1 to 150mg KOH/g paraffin, for high density polyethylene waxes, comprise that not only Alathon wax also comprises polyethylene and amounts to comonomer such as the propylene of 20 weight % at the most, the 1-butylene, the 1-amylene, the 1-hexene, the 1-octene, the copolymer of 1-decene or 1-laurylene, especially so-called paraffinic waxes and isoparaffin paraffin, scale wax (thick paraffinic waxes) for example, the slack wax extract remainder, scale wax (the thick paraffinic waxes of deoiling), half paraffin made from extra care or making with extra care fully (half makes with extra care or refining fully paraffinic waxes) and the paraffin of bleaching (paraffinic waxes of bleaching) deoil.Here paraffinic waxes be meant especially 40-80 ℃, preferably under the room temperature of 50-75 ℃ of fusion, be the paraffin of solid, i.e. branching or not branching, ring-type or preferred acyclic saturated hydrocarbons are the form of saturated hydrocarbons separately or preferred multiple saturated hydrocarbon mixtures.Within the scope of the present invention, paraffinic waxes preferably is made up of the saturated hydrocarbons with 18-45 carbon atom.Within the scope of the present invention, isoparaffin paraffin preferably is made up of the saturated hydrocarbons that per molecule has a 20-60 carbon atom.
Useful water-repelling agent (a) comprises that also per molecule has at least one C 10-C 60Alkyl, preferably has a C 12-C 40The linearity of alkyl or heterocycle, preferred heteroaromatics (a3) below also are abbreviated as compound (a3), C 10-C 60Alkyl is different or preferred identical and be branching or preferably nonbranched.Preferably can the separating out at least one fatty amine when being heated to 120 to 200 ℃ of temperature in the scope or at least a fatty alcohol (have C 10-C 60The amine of alkyl or alcohol) compound (a3).
The compound of general formula I I very particularly preferably:
Figure A20068003395600091
Wherein
R 3Be selected from branching or preferred nonbranched C 10-C 60Alkyl, for example n-C 10H 21, n-C 12H 25, n-C 14H 29, n-C 16H 33, n-C 18H 37, n-C 20H 41, n-C 30H 61, n-C 40H 81, n-C 50H 101, n-C 60H 121And
R 9-OCH 2, R wherein 9Be selected from branching or preferred nonbranched C 10-C 60Alkyl, for example n-C 10H 21, n-C 12H 25, n-C 14H 29, n-C 16H 33, n-C 18H 37, n-C 20H 41, n-C 30H 61, n-C 40H 81, n-C 50H 101, n-C 60H 121Carbon number and corresponding hydrogen number are meant average.
R 4-R 8Different or preferred identical and be selected from hydrogen, R 3, CH 2-OH, CH 2-O-C 1-C 10Alkyl, especially CH 2-OCH 3, CH 2-OC 2H 5, CH 2-O-n-C 4H 9, CH 2-OCH 2CH 2OH, CH 2-OCH 2CH 2O-C 1-C 10Alkyl, especially CH 2-OCH 2CH 2OCH 3, CH 2-OCH 2CH 2OC 2H 5, CH 2-OCH 2CH 2O-n-C 4H 9, CH 2-(OCH 2CH 2) 2O-H, CH 2-(OCH 2CH 2) 2O-C 1-C 10Alkyl, especially CH 2-(OCH 2CH 2) 2OCH 3, CH 2-(OCH 2CH 2) 2OC 2H 5And CH 2-(OCH 2CH 2) 2O-n-C 4H 9
The compound that other special preferred embodiments of compound (a3) are general formula III:
Wherein each variable as above defines.
One embodiment of the invention are used the water-repelling agent (a) of the combination that comprises at least a paraffin (a2) and at least a compound (a3).
The crosslinked organic copolymer (b) of useful particulate form is a Halogen, the preferred not copolymer of Halogen, it can belong to unsaturated comonomer and the free-radical polymerized acquisition of at least a unsaturated comonomer of diolefins at least (crosslinking agent) by making at least a monoene, and it is a particulate form.
The example that the monoene that is used to prepare the crosslinked organic copolymer (b) of particulate form belongs to unsaturated comonomer is a monovinyl aromatic compounds, for example α-Jia Jibenyixi, especially styrene; With the ethylenically unsaturated carboxylic acids C of acrylic or methacrylic acid for example 1-C 10Arrcostab, methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, acrylic acid ethylhexyl, n-BMA, metering system tert-butyl acrylate and methyl methacrylate more specifically.Can also use acrylonitrile.
Useful crosslinking agent for example comprises two or the trivinyl aromatic compounds, for example adjacent divinylbenzene, a divinylbenzene and to divinylbenzene; And by the ethylenically unsaturated carboxylic acids of olefinic unsaturated alcohol esterification, the example is (methyl) acrylic acid allyl ester; And two or (methyl) acrylate of trihydroxylic alcohol, the example is ethylene glycol bisthioglycolate (methyl) acrylate, 1, ammediol two (methyl) acrylate, diethylene glycol (DEG) two (methyl) acrylate, 1,4-butanediol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,1,1-trimethylolpropane two (methyl) acrylate, 1,1,1-trimethylolpropane tris (methyl) acrylate.
The crosslinked organic copolymer (b) of particulate form can by for example use at the most 20mol%, preferred 1-10mol%, more preferably at least the 3mol% crosslinking agent with 80mol%, preferred 90mol% at least at least, more preferably one or more above-mentioned monoene of 97mol% belong to the unsaturated comonomer preparation at the most.
The crosslinked organic copolymer (b) of particulate form can be pulverized copolymer by the shaping particles method that is fit in the synthetic back of reality and obtain, for example by grinding.Also can synthesize like this, produce the copolymer that monoene belongs to unsaturated comonomer or single unsaturated comonomer and crosslinking agent with particulate form, for example by synthesizing with the form of emulsion polymerisation or mini-emulsion polymerization or suspension polymerization.
Particulate form in the scope of the invention is intended to refer to that cross-linked copolymer (b) exists with the particle form of water insoluble or water-bearing media.Described particle can have irregularly shaped or can preferably have regular shape, and is for example oval or spherical, this means to comprise such particle, wherein at least 75 weight %, preferably at least 90 weight % exist with sphere, and other particle exists with granular.
One embodiment of the invention comprise that the crosslinked organic copolymer (b) of particulate form neither exists with aggregate form, does not exist with the agglomerate form again.
One embodiment of the invention comprise that the crosslinked organic copolymer (b) of particulate form has 10-450nm, preferred 20-250nm, the more preferably weight-average diameter in the 50-100nm scope.Particle diameter can adopt for example transmission electron microscope(TEM) measurement of method commonly used.
One embodiment of the invention comprise, the crosslinked organic copolymer (b) of particulate form has uniform grain sizes and distributes, promptly the particle of at least 80 weight % have average diameter ± diameter in 20% scope.
Another embodiment of the invention comprises, the crosslinked organic copolymer (b) of particulate form has bimodal or the size distribution of multimodal more.
One embodiment of the invention comprise, the crosslinked organic copolymer (b) of particulate form has certain thermal dimensional stability, because the crosslinked organic copolymer (b) of particulate form is 30-200 ℃, preferred 120-180 ℃, more preferably 150-170 ℃ of storage, its size is without any the change of measurable degree in 1 second to 30 minutes, preferred period of 3 minutes at the most.
Useful have epoxy radicals, a NH-CH 2The film forming addition copolymer (c) of OH group or acetoacetyl comprises that for example one or more monoene belong to unsaturated comonomer and one or more have epoxy radicals, NH-CH 2It for example is the C of monovinyl aromatic compounds, monoethylenically unsaturated carboxylic acid, monoethylenically unsaturated carboxylic acid that the copolymer of the comonomer of OH group or acetoacetyl, described monoene belong to unsaturated comonomer 1-C 10Arrcostab, monoene belong to the multifunctional derivative of unsaturated carboxylic acid amides, ethylenically unsaturated carboxylic acids.
The example of particularly suitable monovinyl aromatic compounds is α-Jia Jibenyixi, p-methylstyrene, 2,4-dimethyl styrene, especially styrene.
Particularly suitable monoethylenically unsaturated carboxylic acid is for example maleic acid, fumaric acid, E-and Z-crotonic acid, itaconic acid, especially acrylic acid and methacrylic acid.
The C of particularly suitable monoethylenically unsaturated carboxylic acid 1-C 10Arrcostab is branching or nonbranched C 1-C 10The ester of one of alkanol and above-mentioned monoethylenically unsaturated carboxylic acid.Concrete example is: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-BMA, tert-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid 2-ethylhexyl.
It is N methacrylamide, N-methyl acrylamide, N-ethyl acrylamide, N-ethyl-methyl acrylamide, N that particularly suitable monoene belongs to unsaturated carboxylic acid amides, N-DMAA, N, N-dimethylmethacryl amide, especially acrylamide and Methacrylamide.
The multiple functionalized derivative of particularly suitable ethylenically unsaturated carboxylic acids is the compound of general formula I V:
Figure A20068003395600121
Wherein
X 1And X 2Identical or different and be selected from oxygen, NH and N-R 11,
A is basic at interval, for example branching or nonbranched C 2-C 20Alkylidene or phenylene.C 2-C 20The example of alkylidene is-(CH 2) 2-,-CH 2-CH (CH 3)-,-(CH 2) 3-,-CH 2-CH (C 2H 5)-,-(CH 2) 4-,-(CH 2) 5-,-(CH 2) 6-,-(CH 2) 7-,-(CH 2) 8-,-(CH 2) 9-,-(CH 2) 10-; Preferred C 2-C 4-alkylidene; Especially-(CH 2) 2-,-CH 2-CH (CH 3)-,-(CH 2) 3-,-(CH 2) 4-and-CH 2-CH (C 2H 5)-.
R 10And R 11Identical or different and be selected from C 1-C 10Alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, neopentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohesyl, Sec-Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl, more preferably nonbranched C 1-C 4Alkyl such as methyl, ethyl, n-pro-pyl and normal-butyl.
Particularly suitable comonomer with epoxy radicals is for example ethylene oxidic ester of maleic acid, fumaric acid, E-and Z-crotonic acid, especially acrylic acid and methacrylic acid.
Particularly suitable have a NH-CH 2The comonomer of OH group belongs to the product of unsaturated carboxylic acid amides, especially N methacrylamide and N-methylol methacrylamide for for example formaldehyde and monoene.
Particularly suitable comonomer with acetoacetyl is for example (methyl) acrylate of the alcohol of general formula V:
Figure A20068003395600131
Wherein
R 12Be selected from branching or nonbranched C 1-C 10Alkyl, as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, neopentyl, 1,2-dimethyl propyl, isopentyl, n-hexyl, isohesyl, Sec-Hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, positive decyl, more preferably nonbranched C 1-C 4Alkyl such as methyl, ethyl, n-pro-pyl and normal-butyl.
Have epoxy radicals, NH-CH 2The film forming addition copolymer (c) of OH group or acetoacetyl can prepare in a conventional manner, for example in the presence of one or more emulsifying agents by preparing with one or more free radical starting material emulsion polymerisations.Especially preferably the emulsion polymerization prepared by cropping pattern (seeded mode) has epoxy radicals, NH-CH 2The film forming copolymer of OH group or acetoacetyl (c); That is, add for example polystyrene of one or more water-insoluble polymer with very little particle form (for example it has the average diameter of 15-30nm) at first, described then polymer promotes drop to form during combined polymerization.Should will when beginning, copolymerization not obscure with the polymer of very little particle interpolation and the crosslinked organic copolymer (b) of particulate form.
One embodiment of the invention comprise having epoxy radicals, NH-CH 2Film forming addition copolymer (c) viscosity at room temperature of OH group or acetoacetyl is 10-200mPas, is for example measured by Brookfield (Brookfield).
One embodiment of the invention comprise having epoxy radicals, NH-CH 2The glass transition temperature T of the film forming addition copolymer (c) of OH group or acetoacetyl gFor-50 to+30 ℃, be preferably-20 to+30 ℃.
One embodiment of the invention comprise having epoxy radicals, NH-CH 2The per molecule that the film forming addition copolymer (c) of OH group or acetoacetyl has 0.1 weight % to 7 a weight % for example has an epoxy radicals, NH-CH 2The comonomer of the combined polymerization of OH group or acetoacetyl.
A particular of the present invention also comprises with at least a emulsifying agent (d) to be handled.Useful emulsifying agent (d) is anion, CATION and non-ionic surface active compound.
The non-ionic surface active compound that is fit to for ethoxylation for example singly, two and trialkyl phenol (degree of ethoxylation in the 3-50 scope, alkyl group: C 4-C 12) and the fatty alcohol of ethyoxyl (degree of ethoxylation is in the 3-80 scope; Alkyl: C 8-C 36).Example is BASF Aktiengesellschaft's
Figure A20068003395600141
Board or Union Carbide's
Figure A20068003395600142
Board.Other non-ionic surface active compounds that are fit to are those of general formula VI:
Figure A20068003395600143
R 13Be selected from C 6-C 40Alkyl, for example n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, iso-octyl, n-nonyl, positive decyl, isodecyl, n-undecane base, dodecyl, Permethyl 99A base, n-tridecane base, n-tetradecane base, different myristyl, n-pentadecane base, n-hexadecyl, n-octadecane base, n-eicosane base, n-C 30H 61, n-C 40H 81, have the C of the two keys of 1-5 C-C 3-C 40Thiazolinyl, wherein C-C two keys be for example separate or conjugation.Concrete example be allyl ,-(CH 2) 2-CH=CH 2, all-cis formula-(CH 2) 8-(CH=CH-CH 2) 3CH 3, all-cis formula-(CH 2) 8-(CH=CH-CH 2) 2(CH 2) 4CH 3, suitable-(CH 2) 8-CH=CH-(CH 2) 7CH 3,
R 14Identical or different and be selected from hydrogen and methyl, be preferably hydrogen,
M and n are identical or different and be selected from the integer of 0-20, are preferably the integer of 2-12.
The anionic surfactant compound that is fit to for example is an alkyl sulfate (alkyl: C 8-C 12) alkali metal salt and ammonium salt, ethoxylation alkanol (degree of ethoxylation in the 4-30 scope, alkyl: C 12-C 18) and ethoxylated alkylphenol (degree of ethoxylation in the 3-50 scope, alkyl: C 4-C 12) the alkali metal salt of sulfuric acid monoester and ammonium salt, alkyl sulfonic acid (alkyl: C 12-C 18) and alkyl aryl sulphonic acid (alkyl: C 9-C 18) alkali metal salt and ammonium salt.Particularly suitable anionic surfactant compound is the sulfiting C of butanedioic acid 5-C 40The alkali metal salt of alkyl monoester and ammonium salt.
The cation surface activating compound that is fit to is generally and contains C 6-C 18Alkyl, C 6-C 18The salt of uncle ammonium salt, secondary ammonium salt, tertiary amine salt or quaternary ammonium salt, alkanol ammonium salt, pyridiniujm, imidazoline salt, oxazoline salt, alkylbenzyldimethylasaltsum saltsum, thiazoline salt and the amine oxide of aralkyl or heterocyclic radical, quinolinium, isoquinolin salt, Salt, sulfonium salt He phosphonium salt.The example that can mention is acetate dodecyl ammonium or corresponding hydrochloride, various alkanoic acid 2-(N, N, the N-trimethyl ammonium) chloride of ethyl ester or acetate, N-hexadecylpyridinium chloride, N-dodecyl sulphate pyridine, N-cetyl-N, N, N-trimethylammonium bromide, N-dodecyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-alkyl dimethyl ammonium chloride and Gemini surfactant N, N '-(dodecyl dimethyl) ethylenediamine dibromide.Many other examples can be referring to H.Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and referring to McCutcheon ' s, Emulsifiers ﹠amp; Detergents, MC Publishing Company, Glen Rock, 1989.
Pending surface can be handled in a step or multistep with following material:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to one or more emulsifying agents.
Method of the present invention can for example be undertaken by handling pending surface with at least a preferred aqueous formulation, and preferred aqueous formulation comprises:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to one or more emulsifying agents.
Also can use identical or different preferred aqueous formulation to carry out a plurality of treatment steps.
Aqueous formulation can be any required water slurry, preferably liquid, aqueous.
Aqueous formulation, especially liquid, aqueous solids content can be in 10 weight % to 70 weight %, preferred 30 weight % to 50 weight % scopes.
One embodiment of the invention comprise by handling pending surface implements the inventive method, comprise that initial usefulness comprises the preferred aqueous formulation treatment surface of crosslinked organic copolymer (b) of at least a water-repelling agent (a) and another particulate form, subsequently with comprising at least a have epoxy radicals, NH-CH 2The film forming addition copolymer (c) of OH group or acetoacetyl but do not contain the new liquid handling surface of the crosslinked organic copolymer (b) of particulate form.
Another embodiment of the invention comprises by handling pending surface implements the inventive method, comprise that initial usefulness comprises the preferred aqueous formulation treatment surface of the crosslinked organic copolymer (b) of at least a water-repelling agent (a) and other at least a particulate form, subsequently with comprising different water-repelling agent (a) and a kind ofly having epoxy radicals, a NH-CH 2The film forming addition copolymer (c) of OH group or acetoacetyl but do not contain the new preferred aqueous formulation treatment surface of the crosslinked organic copolymer (b) of particulate form.
Another embodiment of the invention comprises by handling pending surface implements the inventive method, comprises that initial usefulness comprises at least a have epoxy radicals, NH-CH 2The preferred aqueous formulation treatment surface of the film forming addition copolymer (c) of OH group or acetoacetyl and the crosslinked organic copolymer (b) of other at least a particulate form is subsequently with the new preferred aqueous formulation treatment surface that comprises water-repelling agent (a).
Another embodiment of the invention comprises by handling pending surface implements the inventive method, comprises that initial usefulness comprises at least a water-repelling agent (a), the crosslinked organic copolymer (b) of at least a particulate form and have epoxy radicals, NH-CH 2The preferred liquid, aqueous treatment surface of the film forming addition copolymer (c) of OH group or acetoacetyl does not comprise yet and has epoxy radicals, NH-CH with neither comprising water-repelling agent (a) subsequently 2The film forming addition copolymer (c) of OH group or acetoacetyl but comprise the new liquid handling surface of the crosslinked organic copolymer (b) of the particulate form that the first step used.
It is not crucial to be used to carry out the temperature itself that the present invention handles.Temperature can be in 10-60 ℃ of scope, preferably in 15-30 ℃ of scope.
Preferred aqueous formulation, especially preferred liquid, aqueous pH can be in the 2-9 scope, preferably in the 3.5-7.5 scope.
For by implementing the present invention, thereby can select hydroscopicity that hydroscopicity makes that the inventive method obtains in 25 weight % to 95 weight % scopes, preferably in 60 weight % to 90 weight % scopes with the pending surface of liquid, aqueous processing.
In one embodiment of the invention, method of the present invention can be carried out in being usually used in the machine of finish fabric, and example is padding mangles (pad-mangle).Preferred vertical fabric charging padding mangles, wherein primary element is two rollers that extruding each other contacts, fabric imports via described roller.On above-mentioned roller, fill preferred aqueous formulation and wet fabric.Pressure causes fabric to be extruded and guarantees constant liquid absorption (add-on).In other preferred padding mangles, fabric at first passes dipping bath and imports, and is upward through two rollers of extruding contact each other subsequently.Under one situation of back, think that also padding mangles has fabric charging vertically upward.Padding mangles is described in for example Hans-Karl Rouette, and " Handbuch derTextilveredlung " is in Deutscher Fachverlag 2003, the 618-620 pages or leaves.
In another embodiment of the invention, pending surface is contacted with aqueous formulation, described aqueous formulation comprises:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to one or more emulsifying agents.
According to contact of the present invention can be for example by the single or multiple spraying, with thin droplet wetting (bedrizzle), overflow (overpour) or be completed for printing.
For the purpose of the present invention, aqueous formulation can comprise one or more organic solvents, for example pure, as methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol (DEG), triethylene glycol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), glycol monomethyl n-butyl ether, glycol monomethyl isobutyl ether, acetate, n-butanol, isobutanol, n-hexyl alcohol and isomers, n-octyl alcohol and isomers, n-dodecanol and isomers.Organic solvent can account for 1 weight % to 40 weight % of the continuous phase of aqueous formulation used according to the invention, preferred 2 weight % to 25 weight %.Aqueous formulation is interpreted as referring to the preparaton that continuous phase is main or all be made of water under limiting case.
After processing of the present invention, with treated dry tack free.Dry can under the temperature in 20-120 ℃ of scope for example, finishing.
For example drying can under atmospheric pressure be carried out.Also can under reduced pressure for example carry out under the pressure in 1-850 millibar scope.
Drying can be utilized heating or heated air stream not, particularly for example the inert gas such as the nitrogen current of heating or not heating.In order to utilize heated air stream, suitable temperature range is for example 30-200 ℃, preferred 120-180 ℃, more preferably 150-170 ℃.
Can then heat-treat after processing of the present invention and drying process, be also referred to as tempering within the scope of the present invention, this heat treatment can be continued operation or batch operation.The duration of temper can be selected in wide region.Temper can be carried out about 1 second to 30 minutes usually, especially at the most 3 minutes duration.Temper is undertaken by the temperature that is heated in 180 ℃ at the most, preferred 150-170 ℃ of scope.Certainly need make the sensitiveness of temperature adaptation formation material of surface treated of temper according to the present invention.
The example of the specific tempering method that is fit to is a hot-air dry.
A particular of the present invention comprises that described preferred aqueous formulation comprises with preferred aqueous formulation treatment surface:
(a) water-repelling agent of 0.1 weight % to 20 weight %, preferred 1 weight % to 15 weight %,
(b) the crosslinked organic copolymer of the particulate form of 1 weight % to 25 weight %, preferred 5 weight % to 15 weight %,
(c) 1 weight % to 25 weight %, preferred 2 weight % to 20 weight %'s has epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) emulsifying agent of 0 weight % to 10 weight %, preferred 0.01 weight % to 5 weight %,
(e) auxiliary agent of total 0 weight % to 50 weight %, preferred 1 weight % to 25 weight %,
All % are based on whole preferred aqueous formulation.
One embodiment of the invention comprise by using the aqueous formulation also comprise one or more auxiliary agents (e) to implement method of the present invention, and auxiliary agent (e) for example is 50 weight % at the most based on whole preferred aqueous formulation.Especially in the time will handling one or more fabric faces, can advantageously comprise one or more auxiliary agents (e) at the preferred aqueous formulation that is used for the object of the invention, in this case, auxiliary agent (e) is selected from biocide, thickener, foam inhibitor, wetting agent, plasticizer, softener (feel modifying agent), filler, crosslinking agent (curing agent) and coalescents.
The example that can be used as the biocide of auxiliary agent (e) is 1, and 2-benzisothiazole-3-ketone (BIT) is (as Avecia Lim's
Figure A20068003395600181
Board is commercially available) and alkali metal salt; Other biocide that is fit to is 2-methyl-2H-isothiazole-3 (MIT) and 5-chloro-2-methyl-2H-isothiazole-3-ketone (CIT).Generally speaking, based on preferred aqueous formulation, the biocide of 10-150ppm is enough.
Useful auxiliary agent (e) also comprises one or more thickeners, and described thickener can be natural or synthetic source.The synthetic thickening agent that is fit to is poly-(methyl) acyclic compound, polycarboxylic acids, polyethers, poly-imines, polyamide and polyurethane, especially the copolymer of (methyl) acrylamide derivative that comprises the formula VII of the acrylamide of acrylic acid, 4 weight % to 15 weight % of 85 weight % to 95 weight % and about 0.01 weight % to 1 weight %
Its molecular weight Mw in 100 000-200 000g/mol scopes, each R wherein 15For methyl or be preferably hydrogen.The example of natural thickener is agar, Irish moss, modified starch and modified cellulose.
The amount of the thickener that comprises can be for example 0 weight % to 10 weight % based on the aqueous formulation that uses in the inventive method, is preferably 0.05 weight % to 5 weight %, 0.1 weight % to 3 weight % more preferably.
As the example of the foam inhibitor of auxiliary agent (e) is to be the polysiloxanes of the not ethoxylation of liquid or monosubstituted ethoxyization or many ethoxylations under the room temperature.
The example that is used as the wetting agent of auxiliary agent (e) is alkyl poly glucoside, alkyl phosphonates, phosphonic acids alkyl phenyl ester, alkylphosphonate and alkyl phenyl phosphate ester.
Example as the plasticizer of auxiliary agent (e) is an ester compounds, and described ester compounds is selected from by the aliphatic series of the complete esterification of alkanol or aromatics binary or the phosphoric acid of polybasic carboxylic acid and single at least alkanol esterification more.
In one embodiment of the invention, alkanol is C 1-C 10Alkanol.
By the aromatics binary of the complete esterification of alkanol or more the preferred embodiment of polybasic carboxylic acid be phthalic acid, M-phthalic acid and the mellitic acid of complete alkanol esterification; Concrete example is di-n-octyl phthalate, 2-nonyl-phthalate ester, phthalate ester decanoate, M-phthalic acid di-n-octyl, M-phthalic acid two ester in the positive ninth of the ten Heavenly Stems, M-phthalic acid two ester in the positive last of the ten Heavenly stems.
By the aliphatic binary of the complete esterification of alkanol or more the preferred embodiment of polybasic carboxylic acid be dimethyl adipate, diethylene adipate, Di-n-butyl Adipate, diisobutyl adipate, dimethyl glutarate, ethyl glutarate, glutaric acid di-n-butyl, glutaric acid diisobutyl ester, dimethyl succinate, diethyl succinate, dibutyl succinate, di-iso-octyl succinate and composition thereof.
By alkanol at least the preferred embodiment of the phosphoric acid of mono-esterification be phosphoric acid C 1-C 10Alkyl two C 6-C 14Aryl ester is as isodecyl diphenyl phosphate.
The example of the plasticizer that other are fit to is by C 1-C 10Alkyl carboxylic acid is the aliphatic series of mono-esterification or aromatics binary or polyalcohol more at least.
By C 1-C 10Alkyl carboxylic acid at least the aliphatic series of mono-esterification or aromatics binary or more the preferred embodiment of polyalcohol be 2,2,4-trimethylpentane-1,3 glycol mono isobutyrate.
Other plasticizer that are fit to are for preferably having the M of 200g/mol wCan be by aliphatic dicarboxylic acid and aliphatic diol polycondensation, for example adipic acid or butanedioic acid and 1, the polyester that the polycondensation of 2-propylene glycol obtains and preferably have the M of 450g/mol wThe polypropylene glycol alkyl phenyl ether.
Other plasticizer that are fit to are by two kinds of pure etherificates of difference and its molecular weight M wPolypropylene glycol in the 400-800g/mol scope, wherein preferred a kind of alcohol can be alkanol, especially C 1-C 10Alkanol, another kind of alcohol can be preferably aromatic alcohol, for example orthoresol, metacresol, paracresol, especially phenol.
The example that is used as the filler of auxiliary agent (e) is the melamine and the pigment of particulate form.
The example that is used as the feel modifying agent of auxiliary agent (e) is an organic silicon emulsion, can preferably have the aqueous emulsion of the polysiloxanes of hydrophilic radical such as OH base or alkoxylate group.
The example that is used as the crosslinking agent (curing agent) of auxiliary agent (e) is the condensation product of urea, glyoxal and formaldehyde, if be fit to, it preferably uses linear C 1-C 4The alkanol etherificate, especially dual, triple or quadruple methyl alcohol or ethanol etherificate
Figure A20068003395600201
Crosslinking agent (curing agent) as auxiliary agent (e) also comprises isocyanuric acid ester, especially the hydrophiling vulcabond/isocyanuric acid ester of hydrophiling isocyanuric acid ester and mixing, for example C 1-C 4The product of the isocyanuric acid ester of alkyl polyethylene glycol and hexamethylene diisocyanate (HDI).The example of the crosslinking agent that this class is fit to is for example known by EP-A 0 486 881.
The example that is used as the film forming agent (coalescents) of auxiliary agent (e) is a diethylene glycol (DEG).
In another embodiment of the invention, use (a) to (c) if be fit to emulsifying agent (d) and if before being fit to auxiliary agent (e) processing, provide at least a priming paint (f) to surface to be coated.Priming paint (f) preferably makes the surface that will handle according to the present invention have electric charge with crosslinked organic copolymer (b) opposite charge of particulate form.For example, when using the cationic crosslinked organic copolymer (b) of particulate form, it is favourable using anionic priming paint (f).Yet when using the crosslinked organic copolymer of anionic (b) of particulate form, it is favourable using cationic priming paint (f).
The priming paint (f) that is fit to can be for for example polymerization or non-polymeric character.The polymer priming paint that is fit to for example can have the number-average molecular weight in the 5000-500 000g/mol scope.
Useful cationic priming paint (f) comprises for example polymine, and especially amino silicones for example has at least one (CH 2) wNH-R 16(w is the integer of the integer of 1-10, especially 2-7 in each case, and R 16Be selected from hydrogen, preferred linear C 1-C 4Alkyl) group and (CH 2) wNH-R 17Group (R 17Be selected from hydrogen, preferred linear C 1-C 4Alkyl) polysiloxanes, and polyvinyl imidazol.Other cationic priming paint (f) that are fit to are diallyl two C 1-C 4The polymer of alkyl ammonium halide, wherein each C 1-C 4Alkyl is preferably linearity.
Other cationic priming paint (f) that are fit to are the product of preferred cyclic diamine and the chloropropylene oxide and the alkylating agent of equimolar amounts, and described alkylating agent for example is a dimethyl suflfate, C 1-C 10Alkyl halide, especially iodomethane, or benzyl halide, especially benzyl chloride.The molecular weight M of this product wCan be in 1000-1 000 000g/mol scope and structure as follows, with reference to the example explanation of the product of the piperazine of equimolar amounts and chloropropylene oxide and benzyl chloride:
The anionic priming paint (f) that is fit to be for example anionic monomer, and especially olefinic unsaturated sulfonic acid, the unsaturated amine oxide of olefinic or (methyl) acrylic acid homopolymers are if or be fit to and the acrylic acid C of one or more (methyl) 1-C 10The copolymer of Arrcostab.Other anionic priming paint that are fit to be for example anion polyurethane, that is, be the polyurethane that per molecule comprises at least one sulfonic group or carboxylic acid group herein, and it can be by for example using 1, and the 1-dihydromethyl propionic acid prepares.
For using one or more priming paint (f), it preferably uses with aqueous formulation and applied before handling with the crosslinked organic copolymer (b) of particulate form.The operating technology that is fit to for example comprises spraying, using carefully drips wetting, especially pad dyeing.
Can apply priming paint (f) and handle before and heat-treat afterwards with the crosslinked organic copolymer (b) of particulate form respectively, heat treated condition be corresponding to aforesaid condition.
One embodiment of the invention comprise cationic priming paint (f) are applied to cotton surface, if be fit to heat treatment, use crosslinked organic copolymer (b), emulsifying agent (c) and the water-repelling agent (a) of particulate form subsequently and have epoxy radicals, NH-CH 2The film forming addition copolymer (c) of OH group or acetoacetyl is handled.Heat-treat after this.
Another embodiment of the invention comprises anionic priming paint (f) is applied to surface of polyester, if be fit to heat treatment, use crosslinked organic copolymer (b), emulsifying agent (c) and the water-repelling agent (a) of particulate form subsequently and has epoxy radicals, NH-CH 2The film forming addition copolymer (c) of OH group or acetoacetyl is handled.Heat-treat after this.
The present invention also provides the surface that applies with following material:
(f) if be fit to, at least a priming paint,
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl.
Can be according to surface of the present invention advantageously by said method production of the present invention.Pollute for having texture and waterproof and being difficult on surface according to the present invention.
One embodiment of the invention only comprise with trace (if the words that have) one or more used emulsifying agents (d) are put on surface of the present invention, and therefore are not present in basically in the surface through applying of the present invention.
One embodiment of the invention only comprise with trace (if the words that have) one or more adjuvant used (e) are put on surface of the present invention, and therefore are not present in basically in the surface through applying of the present invention.
In one embodiment of the invention, surface of the present invention is characterised in that the processing generation can inhomogeneous, preferred coating uniformly.It is regular evenly being intended to fingerprint reason, and uneven be meant crossgrained, texture area and no texture area are promptly arranged on the surface.
In one embodiment of the invention, surface of the present invention has average liquid absorption at 1-10g/m 2In the scope, preferably at 1.5-5g/m 2Coating in the scope.
In one embodiment of the invention, surface of the present invention is a fabric face.
The present invention also provides aqueous formulation, and it comprises:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to, one or more emulsifying agents,
(e) if be fit to one or more auxiliary agents.
In one embodiment of the invention, preferred aqueous formulation of the present invention comprises:
(a) water-repelling agent of 0.1 weight % to 20 weight %, preferred 1 weight % to 15 weight %,
(b) the crosslinked organic copolymer of the particulate form of 1 weight % to 25 weight %, preferred 5 weight % to 15 weight %,
(c) 1 weight % to 25 weight %, preferred 2 weight % to 20 weight %'s has epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) emulsifying agent of 0 weight % to 10 weight %, preferred 0.01 weight % to 5 weight %,
(e) auxiliary agent of total 0 weight % to 50 weight %, preferred 1 weight % to 25 weight %,
All wt percentage is based on the preferred aqueous formulation of whole the present invention.
In one embodiment of the invention, preparaton according to the present invention comprises one or more auxiliary agents (e), preferably 10 weight % at the most.
In one embodiment of the invention, according to the pH of preferred aqueous formulation of the present invention in the 2-9 scope, preferably in the 3.5-7.5 scope.
In one embodiment of the invention, the solids content that preferred aqueous formulation according to the present invention has is in 10 weight % to 70 weight % scopes, preferably in 30 weight % to 50 weight % scopes.
In one embodiment of the invention, according to the dynamic viscosity that has of preferred aqueous formulation of the present invention in the 50-5000mPas scope, in the preferred 100-4000mPas scope, more preferably in the 200-2000mPas scope, for example measure with Brookfield (Brookfield) viscosimeter according to DIN 51562-1 to 4.
In one embodiment of the invention, preferred aqueous formulation according to the present invention comprises crosslinked organic (be total to) polymer (b) of number average diameter in the 10-450nm scope.
Aqueous formulation according to the present invention makes said method of the present invention effective especially, and for example can easily be processed into by dilute with water and make the effective liquid of the inventive method equally.
The present invention also provides the method for a kind of production according to aqueous formulation of the present invention, below is also referred to as production method of the present invention.Production method of the present invention is preferably undertaken by following material is mixed with water:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to, one or more emulsifying agents,
(e) if be fit to one or more auxiliary agents.
Production method of the present invention can use the container of any needs to carry out, preferred stirred vessel.
In the enforcement of the method according to this invention, the interpolation of component water and following material order is not crucial:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to, one or more emulsifying agents,
(e) if be fit to one or more auxiliary agents.Preferably at first water is introduced as initial charge, sneaked into component (a) to (c) then and if be fit to (d) and (e).
Embodiment illustrates the present invention by work.
Use the Coulter counter of Malvern, the particle diameter of measuring the addition copolymer of dispersion or emulsification according to ISO 13321 distributes.
All the time use brookfield's viscometer, measure dynamic viscosity according to DIN 51562-1 to 4.
I. the component for preparing preparaton of the present invention
I.1. synthesize and have NH-CH 2The film forming addition copolymer of OH group, acetoacetyl or epoxy radicals
I.1.1 synthesize and have NH-CH 2The film forming addition copolymer (c.1) of OH group
Prepare following mixture:
Mixture is I.1.1.1:
The complete deionized water of 161g
17.9g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
163.7g the acrylic acid of n-butyl acrylate, 245.2g styrene, the new distillation of 2.8g
12g N-methylol methacrylamide (MAMol), the aqueous solution of 15 weight %.
Mixture is I.1.1.2: the 0.6g Na in the complete deionized water of 100ml 2S 2O 8
Mixture is I.1.1.3: the 0.4g HO-CH in the complete deionized water of 50ml 2-O-SO 2Na
In 5 liters of jars being furnished with agitator, nitrogen connector and three metering devices, pack into and comprise the suspension of complete deionized water of 160ml and 9.1g polystyrene seed (average diameter 30nm, the water slurry of 33 weight %).Make nitrogen pass through suspension 1 hour.Then with mixture heated to 75 ℃.
Begin then to add mixture simultaneously I.1.1.1, mixture I.1.1.2 with mixture I.1.1.3.I.1.1.1, mixture added in 3 hours, and I.1.1.3 I.1.1.2 mixture added in 3 hours 15 minutes with mixture.During adding, temperature maintenance is at 75 ℃.
After finishing interpolation, stirred 30 minutes at 75 ℃, and for deodorizing, with after 90 minutes time be metered into solution and the 0.8g HO-CH of 1.7g t-butyl hydroperoxide (70 weight % in water) in 22ml distilled water simultaneously 2-O-SO 2The solution of Na in 25ml distilled water.
Cool to room temperature adds 1 of 0.5g 20 weight % after this, and the mixture of the propylene glycol solution of 2-benzisothiazole-3-ketone and 10ml distilled water stirred 10 minutes subsequently.
The ammoniacal liquor of using about 4g 25 weight % then is with pH regulator to 6.3.
Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This produces aqueous dispersion Disp.1, and it comprises and has NH-CH 2The film forming addition copolymer (c.1) of OH group.Solids content is 38.7 weight %, and dynamic viscosity is 50mPas.Particle diameter distributes: maximum is at 158nm.
I.1.2. synthetic film forming addition copolymer (c.2) with epoxy radicals
Prepare following mixture:
Mixture is I.1.2.1:
The complete deionized water of 277g
17.9g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
245.2g the methacrylic acid of n-butyl acrylate, 120g styrene, the new distillation of 2.8g
16g glycidyl methacrylate, 16g acrylic acid 2-hydroxyl ethyl ester.
Mixture is I.1.2.2: the 4.0g Na in the complete deionized water of 100ml 2S 2O 8
In 5 liters of jars being furnished with agitator, nitrogen connector and three metering devices, pack into and comprise the suspension of the complete deionized water of 160ml and 9.1g polystyrene seed (average diameter 30nm, the water slurry of 33 weight %) and 0.8g sodium pyrophosphate.Make nitrogen pass through suspension 1 hour.Subsequently with mixture heated to 75 ℃.
Begin then to add simultaneously mixture I.1.2.1 with mixture I.1.2.2.I.1.2.1, mixture added in 3 hours, and I.1.2.2 mixture added in 3 hours 15 minutes.During adding, temperature maintenance is at 75 ℃.
After finishing interpolation, stirred 30 minutes at 75 ℃, and for deodorizing, with after 90 minutes time be metered into solution and the 2g acetone of 2g t-butyl hydroperoxide (70 weight % in water) in 11ml distilled water simultaneously and close the solution of bisulfites (acetone disulfite) in 23.5ml distilled water.
Cool to room temperature adds 1 of 0.5g 20 weight % after this, and the mixture of the propylene glycol solution of 2-benzisothiazole-3-ketone and 10ml distilled water stirred 10 minutes subsequently.
The ammoniacal liquor of using about 4g 25 weight % then is with pH regulator to 5.
Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This produces aqueous dispersion Disp.2, and it comprises the film forming addition copolymer (c.2) with epoxy radicals.Solids content is 39.2 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: maximum is at 157nm.
I.1.3 synthesize and have NH-CH 2The film forming addition copolymer (c.3) of OH group
Prepare following mixture:
Mixture is I.1.3.1:
The complete deionized water of 175g
128g styrene, 2.8g acrylic acid, the 12g N-methylol methacrylamide in 68ml water,
245.2g n-butyl acrylate
8g compound VI .1 (referring to following) in 12ml water
12g N, N-dimethylaminopropyl Methacrylamide (DMAPMAM is referring to following)
Figure A20068003395600271
R 13.1-[N(CH 2CH 2O) 6H] 2 VI.1
R wherein 13.1Be cis-(CH 2) 8-CH=CH-(CH 2) 7CH 3,
Using formic acid to regulate pH is 4.0.
Mixture is I.1.3.2: the 2g 2 in the complete deionized water of 100ml, two (2-amidine propane) dihydrochlorides of 2 '-azo
In 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, pack into comprise the complete deionized water of 250ml, 4g compound VI .1 (being dissolved in the 6ml water), 66g mixture I.1.3.1 with 10.2g mixture emulsion I.1.3.2.Use formic acid with pH regulator to 4.0.Afterwards, make nitrogen by the emulsion that obtains 15 minutes.Emulsion is heated to 75 ℃ subsequently.
Begin then to add simultaneously remaining mixture I.1.3.1 with mixture I.1.3.2.I.1.3.1, remaining mixture added in 2 hours, and I.1.3.2 remaining mixture added in 2 hours 15 minutes.During adding, temperature maintenance is at 75 ℃.
After finishing interpolation, stirred 30 minutes at 75 ℃, and for deodorizing, with after 90 minutes time, be metered into simultaneously with the 1.2g t-butyl hydroperoxide solution (weight 70% in water) of 30ml distilled water diluting with the 1.2g acetone of 30ml distilled water diluting and close bisulfite solution (13 weight % in water).
Cool to room temperature after this.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 1g grumeleuse.
This produces aqueous dispersion Disp.3, and it comprises and has NH-CH 2The film forming addition copolymer (c.3) of OH group.Solids content is 37.0 weight %, and dynamic viscosity is 370mPas.Particle diameter distributes: maximum is at 100nm.
I.2 the crosslinked organic copolymer (b) for preparing particulate form
I.2.1. the crosslinked organic copolymer (b.1) for preparing particulate form
Prepare following mixture:
Mixture is I.2.1.1:
The complete deionized water of 243g
305.2g styrene, 2.8g acrylic acid,
80g ALMA (referring to following)
8g compound VI .1 in 12ml water
12g N, N-dimethylaminopropyl Methacrylamide
Figure A20068003395600281
Allyl methacrylate
Using formic acid is 4.0 with pH regulator.
Mixture is I.2.1.2: the 2g 2 in the complete deionized water of 100ml, two (2-amidine propane) dihydrochlorides of 2 '-azo
In 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, pack into comprise the complete deionized water of 250ml, 4g compound VI .1 (being dissolved in the 6ml water), 66g mixture I.2.1.1 with 10.2g mixture emulsion I.2.1.2.Use formic acid with pH regulator to 4.0.Afterwards, make nitrogen by the emulsion that obtains 15 minutes.Emulsion is heated to 75 ℃ subsequently.
Begin then to add simultaneously remaining mixture I.2.1.1 with mixture I.2.1.2.I.2.1.1, remaining mixture added in 2 hours, and I.2.1.2 remaining mixture added in 2 hours 15 minutes.Holding temperature is at 75 ℃ during adding.
After finishing interpolation, stirred 30 minutes at 75 ℃, and for deodorizing, with after 90 minutes time, be metered into 1.2g t-butyl hydroperoxide solution (70 weight % in water) simultaneously and close bisulfite solution (13 weight % in water) with the 1.2g acetone of 30ml distilled water diluting with the 30ml distilled water diluting.
After this, cool to room temperature.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 0.5g grumeleuse.
This produces aqueous dispersion WD.1, and it comprises the crosslinked organic copolymer (b.1) of particulate form.Solids content is 37.8 weight %, and dynamic viscosity is 35mPas.Particle diameter distributes: maximum is at 91nm.
I.2.2. the crosslinked organic copolymer (b.2) for preparing particulate form
Prepare following mixture:
Mixture is I.2.2.1:
The complete deionized water of 238g
397g styrene
The 100g ALMA
2.8g acrylic acid
28.6g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
Mixture is I.2.2.2: the 2g Na in the complete deionized water of 100ml 2S 2O 8
In 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, pack into and comprise the emulsion of complete deionized water of 240ml and 48.5g polystyrene seed (average diameter 30nm, the water slurry of 33 weight %).Afterwards, make nitrogen by the suspension that obtains 15 minutes.Suspension is heated to 85 ℃ subsequently.
Begin then to add simultaneously mixture I.2.2.1 with mixture I.2.2.2.I.2.2.1, mixture added in 3 hours, and I.2.2.2 mixture added in 3 hours 15 minutes.During adding with temperature maintenance at 85 ℃.
After finishing interpolation, stirred 30 minutes at 85 ℃, and for deodorizing, with after 90 minutes time, be metered into 1.7g t-butyl hydroperoxide solution (70 weight % in water) simultaneously and close bisulfite solution (13 weight % in water) with the 1.5g acetone of 30ml distilled water diluting with the 30ml distilled water diluting.
After this, cool to room temperature.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This produces aqueous dispersion WD.2, and it comprises the crosslinked organic copolymer (b.2) of particulate form.Solids content is 37.2 weight %, pH be 2.0 and dynamic viscosity be 30mPas.Particle diameter distributes: maximum is at 108nm.
I.2.3. the crosslinked organic copolymer (b.3) for preparing particulate form
Prepare following mixture:
Mixture is I.2.3.1:
The complete deionized water of 380g
400g styrene
The 100g ALMA
16.7g the sodium pyrophosphate aqueous solution of 3 weight %
26.8g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
Mixture is I.2.3.2: the 5g Na in the complete deionized water of 100ml 2S 2O 8
In 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, pack into and comprise the n-C of the complete deionized water of 250ml, 8.9g 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution, 139g mixture I.2.3.1 with 10.5g mixture emulsion I.2.3.2.Afterwards, make nitrogen by the emulsion that obtains 15 minutes.Emulsion is heated to 85 ℃ subsequently.
Begin then to add simultaneously remaining mixture I.2.2.1 with mixture I.2.2.2.I.2.2.1, remaining mixture added in 3 hours, and I.2.2.2 remaining mixture added in 3 hours 15 minutes.During adding with temperature maintenance at 85 ℃.
After finishing interpolation, stirred 30 minutes at 85 ℃, and for deodorizing, with after 90 minutes time, be metered into 2.1g t-butyl hydroperoxide solution (70 weight % in water) simultaneously and close bisulfite solution (13 weight % in water) with the 11.5g acetone of 30 ml distilled waters dilution with the 30ml distilled water diluting.
After this, cool to room temperature.Using the ammoniacal liquor of 25 weight % is 8.0 with pH regulator.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This produces aqueous dispersion WD.3, and it comprises the crosslinked organic copolymer (b.3) of particulate form.Solids content is 38 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: maximum is at 79nm.
I.2.4. the crosslinked organic copolymer (b.4) for preparing particulate form
Repeat I.2.3 the only different n-C that use 3.6g (not being 8.9g) 28 weight % when being initial charge 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution.
This produces aqueous dispersion WD.4, and it comprises the crosslinked organic copolymer (b.4) of particulate form.Solids content is 37.7 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: maximum is at 122nm.
I.2.5. the crosslinked organic copolymer (b.5) for preparing particulate form
Prepare following mixture:
Mixture is I.2.5.1:
The complete deionized water of 313g
470g styrene
42.7g the N hydroxymethyl acrylamide aqueous solution of 35 weight %
The 15g 1,4 butanediol diacrylate
16.7g the sodium pyrophosphate aqueous solution of 3 weight %
35.7g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
Mixture is I.2.2.2: the 2.5g Na in the complete deionized water of 100ml 2S 2O 8
The suspension of the polystyrene seed (average diameter 30nm is in water) that comprises complete deionized water of 300ml and 45.5g 33 weight % of in 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, packing into.Afterwards, make nitrogen pass through suspension 15 minutes.Suspension is heated to 85 ℃ subsequently.
Begin then to add simultaneously mixture I.2.5.1 with mixture I.2.5.2.I.2.5.1, mixture added in 3 hours, and I.2.5.2 mixture added in 3 hours 15 minutes.During adding with temperature maintenance at 85 ℃.
After finishing interpolation, stirred 30 minutes at 85 ℃, and for deodorizing, with after 90 minutes time, be metered into 1.4g t-butyl hydroperoxide solution (70 weight % in water) simultaneously and close bisulfite solution (13 weight % in water) with the 1.5g acetone of 25ml distilled water diluting with the 30ml distilled water diluting.
After this, cool to room temperature.Using the ammoniacal liquor of 25 weight % is 7 with pH regulator.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This produces aqueous dispersion WD.5, and it comprises the crosslinked organic copolymer (b.5) of particulate form.Solids content is 37.9 weight %, and dynamic viscosity is 32mPas.Particle diameter distributes: maximum is at 117nm.
I.2.6. the crosslinked organic copolymer (b.6) for preparing particulate form
Prepare following mixture:
Mixture is I.2.6.1:
The complete deionized water of 334g
400g styrene,
The 100g 1,4 butanediol diacrylate
35.7g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
Mixture is I.2.6.2: the 2.5g Na in the complete deionized water of 100ml 2S 2O 8
The suspension of the polystyrene seed (average diameter 30nm is in water) that comprises complete deionized water of 300ml and 60.6g 33 weight % of in 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, packing into.Afterwards, make nitrogen pass through suspension 15 minutes.Suspension is heated to 85 ℃ subsequently.
Begin then to add simultaneously mixture I.2.6.1 with mixture I.2.6.2.I.2.6.1, mixture added in 3 hours, and I.2.6.2 mixture added in 3 hours 15 minutes.During adding with temperature maintenance at 85 ℃.
After finishing interpolation, stirred 30 minutes at 85 ℃, and for deodorizing, with after 90 minutes time, be metered into 1.4g t-butyl hydroperoxide solution (70 weight % in water) simultaneously and close bisulfite solution (13 weight % in water) with the 1.5g acetone of 25ml distilled water diluting with the 30ml distilled water diluting.
After this, cool to room temperature.Using the ammoniacal liquor of 25 weight % is 7 with pH regulator.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This produces aqueous dispersion WD.6, and it comprises the crosslinked organic copolymer (b.6) of particulate form.Solids content is 38 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: maximum is at 111nm.
I.2.7. the crosslinked organic copolymer (b.7) for preparing particulate form
Prepare following mixture:
Mixture is I.2.7.1:
The complete deionized water of 238g
377g styrene, 2.8g acrylic acid
The 20g 1,4 butanediol diacrylate
28.6g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
Mixture is I.2.7.2: the 2.0g Na in the complete deionized water of 100ml 2S 2O 8
The suspension of the polystyrene seed (average diameter 30nm is in water) that comprises complete deionized water of 300ml and 48.5g 33 weight % of in 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, packing into.Afterwards, make nitrogen pass through suspension 15 minutes.Suspension is heated to 85 ℃ subsequently.
Begin then to add simultaneously mixture I.2.7.1 with mixture I.2.7.2.I.2.7.1, mixture added in 3 hours, and I.2.7.2 mixture added in 3 hours 15 minutes.During adding with temperature maintenance at 85 ℃.
After finishing interpolation, stirred 30 minutes at 85 ℃, and for deodorizing, with after 90 minutes time, be metered into 1.4g t-butyl hydroperoxide solution (70 weight % in water) simultaneously and close bisulfite solution (13 weight % in water) with the 1.5g acetone of 25ml distilled water diluting with the 30ml distilled water diluting.
After this, cool to room temperature.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This generation pH is 2.0 aqueous dispersion WD.7, and it comprises the crosslinked organic copolymer (b.7) of particulate form.Solids content is 37.4 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: maximum is at 105nm.
I.2.8. the crosslinked organic copolymer (b.8) for preparing particulate form
Repeat I.2.7, I.2.8.1 different is to use mixture, and it has following composition:
The complete deionized water of 238g
377g styrene, 2.8g acrylic acid,
The 40g 1,4 butanediol diacrylate
28.6g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution.
This generation pH is 2.0 aqueous dispersion WD.8, and it comprises the crosslinked organic copolymer (b.8) of particulate form.Solids content is 37.5 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: maximum is at 108nm.
I.2.9. the crosslinked organic copolymer (b.9) for preparing particulate form
Repeat I.2.7, I.2.9.1 different is to use mixture, and it has following composition:
The complete deionized water of 238g
377g styrene, 2.8g acrylic acid
The 60g 1,4 butanediol diacrylate
28.6g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution.
This generation pH is 2.0 aqueous dispersion WD.9, and it comprises the crosslinked organic copolymer (b.9) of particulate form.Solids content is 37.1 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: maximum is at 108nm.
I.2.10. the crosslinked organic copolymer (b.10) for preparing particulate form
Prepare following mixture:
Mixture is I.2.10.1:
The complete deionized water of 311g
450g styrene
10g 1,3-divinylbenzene, 25g ALMA
42.9g the N hydroxymethyl acrylamide aqueous solution of 35 weight %
35.7g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
Mixture is I.2.10.2: the 2.5g Na in the complete deionized water of 100ml 2S 2O 8
The suspension of the polystyrene seed (average diameter 30nm is in water) that comprises complete deionized water of 300ml and 15.2g 33 weight % of in 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, packing into.Afterwards, make nitrogen by the suspension that obtains 15 minutes.Suspension is heated to 85 ℃ subsequently.
Begin then to add simultaneously mixture I.2.10.1 with mixture I.2.10.2.I.2.10.1, mixture added in 3 hours, and I.2.10.2 mixture added in 3 hours 15 minutes.During adding with temperature maintenance at 85 ℃.
After finishing interpolation, stirred 30 minutes at 85 ℃, and for deodorizing, with after 90 minutes time, be metered into 1.4g t-butyl hydroperoxide solution (70 weight % in water) simultaneously and close bisulfite solution (13 weight % in water) with the 1.5g acetone of 25ml distilled water diluting with the 30ml distilled water diluting.
After this, cool to room temperature.Using the ammoniacal liquor of 25 weight % is 7 with pH regulator.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This produces aqueous dispersion WD.10, and it comprises the crosslinked organic copolymer (b.10) of particulate form.Solids content is 37.6 weight %, and dynamic viscosity is 32mPas.Particle diameter distributes: maximum is at 157nm.
I.2.11. the crosslinked organic copolymer (b.11) for preparing particulate form
Repeat I.2.10, I.2.11.1 different is to use mixture, and it has following composition:
The complete deionized water of 311g
450g styrene
75g 1, the 3-divinylbenzene
42.9g the N hydroxymethyl acrylamide aqueous solution of 35 weight %
35.7g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution.
This generation pH is 7.0 aqueous dispersion WD.11, and it comprises the crosslinked organic copolymer (b.11) of particulate form.Solids content is 37.2 weight %, and dynamic viscosity is 32mPas.Particle diameter distributes: maximum is at 117nm.
I.2.12. the crosslinked organic copolymer (b.12) for preparing particulate form
Repeat I.2.8, I.2.12.1 different is to use mixture, and it has following composition:
The complete deionized water of 238g
377g styrene, 2.8g acrylic acid
The 60g ALMA
28.6g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution.
This generation pH is 2.0 aqueous dispersion WD.12, and it comprises the crosslinked organic copolymer (b.12) of particulate form.Solids content is 37.2 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: maximum is at 108nm.
I.2.13. the crosslinked organic copolymer (b.13) for preparing particulate form
Prepare following mixture:
Mixture is I.2.13.1:
The complete deionized water of 200g
150g styrene, 256.6g n-butyl acrylate, 3.5g acrylic acid
The 45g 1,4 butanediol diacrylate
35.7g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
Mixture is I.2.13.2:
The complete deionized water of 68g
25g styrene, the 15g N-methylol methacrylamide in 85ml water
The 5g 1,4 butanediol diacrylate
7.1g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
Mixture is I.2.13.3: the 2.5g Na in the complete deionized water of 100ml 2S 2O 8
The suspension of the polystyrene seed (average diameter 30nm is in water) that comprises complete deionized water of 300ml and 60.6g 33 weight % of in 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, packing into.Afterwards, make nitrogen by the suspension that obtains 15 minutes.Suspension is heated to 85 ℃ subsequently.
After this, the beginning add simultaneously mixture I.2.13.1 with mixture I.2.13.3.I.2.13.1, mixture added in 2 hours 30 minutes, and I.2.13.3 mixture added in 3 hours 15 minutes.During adding with temperature maintenance at 85 ℃.After mixture interpolation is I.2.13.1 finished, begin immediately to add mixture I.2.13.2, it added in 30 minutes.
After finishing interpolation, stirred 30 minutes at 85 ℃, and for deodorizing, with after 90 minutes time, be metered into 1.4g t-butyl hydroperoxide solution (70 weight % in water) simultaneously and close bisulfite solution (13 weight % in water) with the 1.5g acetone of 25ml distilled water diluting with the 30ml distilled water diluting.
Subsequently this batch of material is cooled to room temperature.Using the ammoniacal liquor of 25 weight % is 7 with pH regulator.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This produces aqueous dispersion WD.13, and it comprises the crosslinked organic copolymer (b.13) of particulate form.Solids content is 37.7 weight %, and dynamic viscosity is 32mPas.Particle diameter distributes: maximum is at 101nm.
I.2.14. the crosslinked organic copolymer (b.14) for preparing particulate form
Prepare following mixture:
Mixture is I.2.14.1:
The complete deionized water of 209g
178.6g methyl methacrylate, 141.7g n-butyl acrylate, 8g methacrylic acid
The 60g 1,4 butanediol diacrylate
1.5g n-C in 2.3ml water 16H 33O (CH 2CH 2O) 7H
Mixture is I.2.14.2: the 2.4g Na in the complete deionized water of 31ml 2S 2O 8
In 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, pack into the emulsion of the polystyrene seed (average diameter 30nm is in water), 5.3g n-butyl acrylate and the 6.5g methyl methacrylate that comprise the complete deionized water of 468ml, 1.8g 33 weight %.Afterwards, make nitrogen by the emulsion that obtains 15 minutes.Subsequently emulsion liquid is heated to 85 ℃ and add the 3.4g mixture I.2.14.2.Stirred 15 minutes in addition at 85 ℃.
Afterwards, the beginning add simultaneously mixture I.2.14.1 with remaining mixture I.2.14.2.I.2.14.1, mixture added in 2 hours, and I.2.14.2 remaining mixture added in 2 hours 15 minutes.During adding with temperature maintenance at 85 ℃.
After finishing interpolation, stirred 30 minutes at 85 ℃, and for deodorizing, with after 60 minutes time, be metered into solution and the 0.7g acetone that the 0.4g t-butyl hydroperoxide is dissolved in the 3.6ml distilled water simultaneously and close bisulfite solution (13 weight % in water).
Cool to room temperature and add the ammonia spirit of 2.4g 25 weight % after this.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 2g grumeleuse.
This generation pH is 9.2 aqueous dispersion WD.14, and it comprises the crosslinked organic copolymer (b.14) of particulate form.Solids content is 34 weight %, and dynamic viscosity is 30mPas.Particle diameter distributes: maximum is at 252nm.
I.3 produce aqueous formulation of the present invention
Use following composition:
The CH of the methacrylic acid of 10 weight % and 90 weight % 2=CHCOO-CH 2-CH 2-O-n-C 6F 13Random copolymer aqueous dispersion (solids content is 20 weight %) (a1.1), its M nBe 30000g/mol (GPC),
Paraffinic waxes (nonbranched, fusion range 65-70 ℃, the average carbon atom number of per molecule: 40) (a2.1)
(d.1): the product of oleyl amine and 6 equivalent ethylene oxides
(e.1): white oil,
(e.2): the compound of following formula:
Figure A20068003395600381
The component of table 1 is sneaked in the stirred vessel, and if be fit to, water is supplemented to 1 liter to obtain aqueous formulation of the present invention F.1 extremely F.3.
Aqueous formulation of the present invention F.1 (b) particle in does not F.3 have the agglomeration tendency.
Form with Disp.1 is added (c.1), adds (b.1) or the like with the form of WD.1.The amount of every kind of solid is recorded in the table.
Table 1: the composition of aqueous formulation of the present invention
Numbering (a) (b) (c) (d) (e)
F.1 70.9g(a1.1) 106.3g(b.1) 70.9g(c.3) ＊ -
F.2 114.5g(a2.1)， 48g(a3.1) 44g(b.1) 46.5g(c.3) ＊ ， 7.5g(d.1) 13g(e.1)， 199.7g(e.2)
F.3 70.9g(a1.1) 106.3g(b.3) 70.9g(c.1) ＊＊ -
*: the compound VI .1 of preparation (b.1), the n-C of preparation (c.3) 12H 25(OCH 2CH 2) 3OSO 3Na
*The n-C of preparation (b.3) and (c.1) 12H 25(OCH 2CH 2) 3OSO 3Na
I.4 prepare anionic priming paint (f A.1)
Prepare following mixture:
Mixture is I.4.1:
The complete deionized water of 146g
130.8g styrene, 245.2g n-butyl acrylate, 12g acrylic acid,
17.9g the n-C of 28 weight % 12H 25(OCH 2CH 2) 3OSO 3The Na aqueous solution
Be dissolved in the 12g N-methylol methacrylamide in the 68g water,
Mixture is I.4.2: the 0.6g Na in the complete deionized water of 100ml 2S 2O 8
Mixture is I.4.3: the 0.4g HO-CH in the complete deionized water of 100ml 2SO 2Na
The suspension of the polystyrene seed (average diameter 30nm is in water) that comprises complete deionized water of 160ml and 9.1g 33 weight % of in 5 liters of jars being furnished with anchor agitator, nitrogen connector and three metering devices, packing into.Make nitrogen pass through suspension 1 hour.Suspension is heated to 75 ℃ subsequently.
I.4.2 and I.4.3 afterwards, I.4.1 beginning adds mixture simultaneously.I.4.1, mixture added in 3 hours, and I.4.2 and I.4.3 mixture adds in each comfortable 3 hours 15 minutes.During adding with temperature maintenance at 75 ℃.
After finishing interpolation, stirred 30 minutes at 75 ℃, and for deodorizing, with after 90 minutes time, be metered into simultaneously with the 1.2g t-butyl hydroperoxide solution (70 weight % in water) of 22ml distilled water diluting with the 0.8g HO-CH of 25ml distilled water diluting 2SO 2Na solution.
The ammoniacal liquor that subsequently this batch of material is cooled to room temperature and uses 25 weight % is with pH regulator to 7.5.Subsequently can thus obtained dispersion via the net filtration of 125 μ m.Filtered 4 minutes consuming time.It removes about 1g grumeleuse.
This generation pH is 7.5 priming paint (f A.1) aqueous dispersion.Solids content is 39.6 weight %, and dynamic viscosity is 310mPas.Particle diameter distributes: maximum is at 216nm.
The piperazine of equimolar amounts and the product of chloropropylene oxide and benzyl chloride are used as cationic priming paint (f K.1), its molecular weight M wBe 15000g/mol.
II. fabric surface treatments of the present invention
Use following fabric:
Cotton: 1m * 30cm, 100% cotton weaven goods, bleaching, mercerising is not handled, twill construction, Unit Weight 196g/m 2(Co);
Polyester: 1m * 30cm, polyester staple fiber weaven goods, Unit Weight 220g/m 2(PES).
All use following equipment in all cases:
Padding mangles: make HVF12085 type, contact pressure 1-3 crust by Mathis.Unless otherwise indicated, otherwise the contact pressure of setting in all cases makes that all hydroscopicity (based on fibre weight) is 60% under the polyester situation, be 90% under cotton situation.Unless otherwise indicated, otherwise liquid be under the room temperature.
Drying machine: from the continuous drier of Mathis THN 12589.
Method of testing:
Spray test: AATCC 22-2001, grease proofing grading (oil rating): AATCC 118-2002,
Hydrophobization: AATCC 193-2004, smoothness: AATCC 124-2001,
Wash conditions: 30 ℃ of meticulous circulations down, the gentle laundry detergent compositions of 15g/l,
Rinsing maching: Miele Novotronic T440C, set: rotary drying, manual flatiron dehumidifying (handion moist).
II.1 with two the step or more multistep carry out fabric surface treatments of the present invention-production Co.1 and PES.1
General operation requires:
Use is according to liquid, aqueous pad dyeing fabric (Co or the PES) (step 1) of table 2.The liquid pad dyeing of on stenter, also using subsequently according to table 2 in two minutes (step 2) after this in 110 ℃ of dryings.Afterwards, in drying machine in the 160 ℃ of fabric treating that will handle thus 2 minutes.This produces the fabric of the present invention according to table 2.
Liquid, aqueously by water table 2 component is mixed (dilution) and produce to 1 liter.
Hydrophobization isocyanuric acid ester/vulcabond of EP 0 486 881 embodiment 4 is used as auxiliary agent (e.4).
II.2 with two the step or more multistep carry out the priming paint fabric surface treatments-production PES.2 that has of the present invention
The initial use comprises the cationic priming paint (f of 8.3g/l K.1) liquid, aqueous pad dyeing PES.Hydroscopicity is 60%, and liquid absorption is 0.5g (f K.1)/m 2PES.After this in drying machine in 120 ℃ of heat treatments 2 minutes.
Use liquid, aqueous pad dyeing (step 1) after this according to table 2.On stenter, so that being 6 weight %, residual moisture content also uses liquid pad dyeing (step 2) subsequently after this according to table 2 in 110 ℃ of dryings two minutes.Afterwards, in drying machine in the 160 ℃ of fabric treating that will handle thus 2 minutes.This produces the fabric of the present invention according to table 2.
Liquid, aqueously by water the preparaton of the present invention of table 2 is mixed (dilution) and produce to 1 liter.
Hydrophobization isocyanuric acid ester/vulcabond of EP 0 486 881 embodiment 4 is used as auxiliary agent (e.4).
II.3 carries out fabric surface treatments of the present invention-production Co.2 and Co.7 with a step
Use is according to the liquid, aqueous pad dyeing Co of table 2.After this on the stenter in 110 ℃ of dryings 2 minutes so that residual moisture content be 7% and subsequently in drying machine in 160 ℃ of heat treatments 2 minutes.This produces fabric Co.2 of the present invention or Co.7 according to table 2.
To produce Co.3 of the present invention and Co.7, different is that used parent material is 1m * 30cm according to the program of table 2 in repetition, the 100% cotton thing of making, bleaching, mercerising is handled, twill construction, and Unit Weight is 120g/m 2And heat-treat 150 ℃ (not being 160 ℃).This produces fabric Co.3 of the present invention or Co.7.The spray test result is 90, and the smoothness result is DP 3.25 (Co.3) and 3.5 (Co.7)
II.4 with two the step or more multistep carry out surface treatment-production PES.3 that the priming paint fabric is arranged of the present invention
The initial use comprises 8.3g/l anionic priming paint (f A.1) liquid, aqueous pad dyeing PES.Hydroscopicity is 60%, and liquid absorption is 0.5g (f A.1)/m 2PES.After this in drying machine in 120 ℃ of heat treatments 2 minutes.
Use liquid, aqueous pad dyeing (step 1) after this according to table 2.After this on the stenter in 110 ℃ of dryings two minutes so that residual moisture content be 6 weight % and in drying machine, handled 2 minutes subsequently in 160 ℃.This produces the fabric PES.3 of the present invention according to table 2.
Liquid, aqueously by water the preparaton of the present invention of table 2 is mixed (dilution) and produce to 1 liter.II.5 with two the step or more multistep carry out fabric surface treatments of the present invention-production Co.4 and PES.4
Use is according to the liquid, aqueous pad dyeing Co (step 1) of table 2.The liquid pad dyeing of on stenter, also using subsequently according to table 2 in two minutes (step 2) after this in 110 ℃ of dryings.Afterwards, in drying machine in the 160 ℃ of fabric treating that will handle thus 2 minutes.This produces the fabric Co.4 of the present invention according to table 2.
Liquid, aqueously by water table 2 component is mixed (dilution) and produce to 1 liter.
II.6 with two the step or more multistep carry out surface treatment-production Co.5 and Co.6 that the priming paint fabric is arranged of the present invention
The initial use comprises the cationic priming paint (f of 5g/l K.1) liquid, aqueous pad dyeing Co.Hydroscopicity is 90%, and liquid absorption is 0.5g (f K.1)/m 2PES.After this in drying machine in 140 ℃ of heat treatments 2 minutes.Use liquid, aqueous pad dyeing (step 1) after this according to table 2.The liquid pad dyeing of on stenter, also using subsequently according to table 2 in two minutes (step 2) after this in 110 ℃ of dryings.Afterwards, in drying machine in the 160 ℃ of fabric treating that will handle thus 2 minutes.This produces fabric Co.5 of the present invention or Co.6 according to table 2.
Liquid, aqueously by water table 2 component is mixed (dilution) and produce to 1 liter.
Hydrophobization isocyanuric acid ester/vulcabond of EP 0 486 881 embodiment 4 is used as auxiliary agent (e.4).
Figure A20068003395600421
Figure A20068003395600431

Claims (17)

1, a kind of method of treatment surface, it comprises with the described surface of following mass treatment:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to, one or more emulsifying agents,
Be dried subsequently.
2, according to the process of claim 1 wherein that described surface is a fabric face.
3, according to the method for claim 1 or 2, the weight-average diameter of wherein said crosslinked organic copolymer (b) is in the 10-450nm scope.
4,, wherein under the temperature in 120-180 ℃ of scope after the drying, handle described surface according to each method among the claim 1-3.
5, according to each method among the claim 1-4, wherein said at least a water-repelling agent (a) is selected from:
(a1) Halogen organic (being total to) polymer,
(a2) paraffin and
(a3) per molecule has at least one C 10-C 60The compound of alkyl.
6, according to each method among the claim 1-5, wherein handle described surface with aqueous formulation, described aqueous formulation comprises:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to one or more emulsifying agents.
7, according to each method among the claim 1-6, wherein said processing is carried out in the presence of one or more auxiliary agents (e).
8, according to each method among the claim 1-7, wherein before carrying out described processing, apply priming paint (f) with following material:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to, one or more emulsifying agents,
(e) if be fit to one or more auxiliary agents.
9, the surface of the following material coating of a kind of usefulness:
(a) if be fit to, priming paint,
(b) at least a water-repelling agent,
(c) the crosslinked organic copolymer of at least a particulate form,
(d) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl.
10, according to the surface of claim 9, the average liquid absorption that wherein said coating has is at 0.2-10g/m 2In the scope.
11, according to the surface of claim 9 or 10, it comprises fabric face.
12, according to each surface among the claim 9-11, the weight-average diameter of wherein said crosslinked organic (being total to) polymer (b) is in the 10-450nm scope.
13, according to each surface among the claim 9-12, wherein said at least a water-repelling agent (a) is selected from:
(a1) Halogen organic (being total to) polymer,
(a2) paraffin and
(a3) per molecule has at least one C 10-C 60The compound of alkyl.
14, a kind of aqueous formulation, it comprises:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to, one or more emulsifying agents,
(e) if be fit to one or more auxiliary agents.
15, according to the aqueous formulation of claim 14, the weight-average diameter of wherein said crosslinked organic (being total to) polymer (b) is in the 10-450nm scope.
16, according to the aqueous formulation of claim 14 or 15, wherein said at least a water-repelling agent (a) is selected from:
(a1) Halogen organic (being total to) polymer,
(a2) paraffin and
(a3) per molecule has at least one C 10-C 60The compound of alkyl.
17, a kind of method of producing according to each aqueous formulation among the claim 14-16, it comprises following material is mixed with water:
(a) at least a water-repelling agent,
(b) the crosslinked organic copolymer of at least a particulate form,
(c) at least a have epoxy radicals, a NH-CH 2The film forming addition copolymer of OH group or acetoacetyl,
(d) if be fit to, one or more emulsifying agents,
(e) if be fit to one or more auxiliary agents.
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